CN105754318B - A kind of compositions of thermosetting resin and its application - Google Patents
A kind of compositions of thermosetting resin and its application Download PDFInfo
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- CN105754318B CN105754318B CN201410809856.3A CN201410809856A CN105754318B CN 105754318 B CN105754318 B CN 105754318B CN 201410809856 A CN201410809856 A CN 201410809856A CN 105754318 B CN105754318 B CN 105754318B
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L71/00—Compositions of polyethers obtained by reactions forming an ether link in the main chain; Compositions of derivatives of such polymers
- C08L71/08—Polyethers derived from hydroxy compounds or from their metallic derivatives
- C08L71/10—Polyethers derived from hydroxy compounds or from their metallic derivatives from phenols
- C08L71/12—Polyphenylene oxides
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/04—Layered products comprising a layer of synthetic resin as impregnant, bonding, or embedding substance
Abstract
The present invention provides a kind of compositions of thermosetting resin, including thermosetting resin and olefin(e) compound containing unsaturated bond.The present invention is cooperated by olefin(e) compound of the selection containing two or more unsaturated bonds such as alkenyl and alkynyl and the thermosetting resin containing unsaturated bond, has obtained a kind of compositions of thermosetting resin with superior dielectric performance.The compositions of thermosetting resin is provided with outstanding heat resistance, production and processing performance and drill processability on the basis of guaranteeing excellent dielectric properties.Compositions of thermosetting resin of the present invention is other than it may be used as preparing resin sheet, resin laminated metal foil, prepreg, laminate, metal-clad laminate and printed wiring board, it can also be used to prepare adhesive, coating, can be used for building, aviation, ship and auto industry.
Description
Technical field
The present invention relates to a kind of compositions of thermosetting resin more particularly to a kind of compositions of thermosetting resin and its in resin
Application in sheet material, resin laminated metal foil, prepreg, laminate, metal-clad laminate and printed wiring board etc..
Background technique
In recent years, as computer and information communication device are fast-developing, for high-speed transfer and processing bulk information, behaviour
Tend to high frequency as signal, meanwhile, in order to meet the use and development trend of each electronic product, circuit board towards high multilayer,
The direction of high density interconnection is developed, this requires baseplate material not only, and there is low-k and low dielectric loss angle tangent to meet
The high-frequency transmission of signal, and to have good heat resistance, processability and superior reliability.It is suitable for printed circuit board at present
In the material of substrate, binder with epoxy resin as main part is widely used.Circuit substrate made from such epoxy has higher
Dielectric constant (4.4 or so) and dielectric loss angle tangent (0.02 or so), be not able to satisfy the requirement of signal high frequency.
The use for not being able to satisfy high frequency in view of the excessively high dielectric constant of ordinary epoxy resin and dielectric loss angle tangent is wanted
It asks, people are also finding the material with lower dielectric constant and dielectric loss angle tangent, such as thermoplastic fluorine-containing resinoid (poly- four
Vinyl fluoride), but since the general melting temperature of fluororesin and melt viscosity are high, extrusion forming must carry out at high temperature under high pressure, and
When making the printed circuit board of high multilayer, there is that processability, dimensional stability and hole metallization are insufficient.
For the deficiency of fluororesin, also just become research hotspot instead of the research work of fluororesin.Polyphenylene oxide has excellent
Different dielectric constant and dielectric loss performance, but the equally high deficiency there is also melting temperature height and melt viscosity, guarantee it is excellent
All electrical properties, mechanical performance (high peel strength of copper foil and dimensional stability etc.) are difficult to ensure while different dielectric properties.
In addition machinability is poor in terms of manufacturing processing, easily causes and scraps, qualification rate is low.
In order to obtain the circuit base material for meeting the requirement of signal high frequency, art technology worker has been carried out largely
It attempts, it is expected that other processabilities, reliability are also optimal on the basis of meeting excellent dielectric properties, but final all difficult
In reaching or keep excellent dielectric properties, but heat resistance is insufficient or excellent heat resistance but poor in processability.
United States Patent (USP) US5932682 is disclosed using the bifunctional epoxy resin containing ketal or acetal chain, but it is substantially still
Belong to two functional epoxy resins of strand both ends, belong to epoxylite, it is difficult to meet the requirement of signal high frequency.Currently without
Such ketal or acetal chain are modified, its compound is made to contain minimum two or more unsaturated bonds such as alkenyl and alkynes
Base is used as curing agent or the report that can meet the requirement of electronic equipment high frequency is made in polymerized monomer.
Summary of the invention
Aiming at the problem that prior art, one of the objects of the present invention is to provide a kind of compositions of thermosetting resin, are used for
The problems such as solving insufficient thermoset polymer dielectric performance in the prior art, poor in processability and poor reliability is obtaining excellent Jie
While electrical property, it may have outstanding heat resistance, production and processing property and drilling processing performance.
In order to achieve the above object, present invention employs following technical solutions:
A kind of compositions of thermosetting resin, including thermosetting resin and olefin(e) compound containing unsaturated bond, the alkene
Hydrocarbon compound has following molecular structural formula:
Wherein, R1And R2It independently is hydrogen atom, alkyl, naphthenic base, heterocycle, Heterocyclylalkyl, alkenyl, cycloalkenyl, fragrance
Base, heteroaryl perfume base, alkane miscellaneous alkyl, alkynyl, alkylene, the miscellaneous alkylene of sub- hydrocarbon, alkenylene, the miscellaneous alkenylene of sub- hydrocarbon, alkynylene or Asia
Any one in the miscellaneous alkynylene of hydrocarbon；R1And R2It may be the same or different；
R3And R4It independently is alkylene, the miscellaneous alkylene of sub- hydrocarbon, alkenylene, the miscellaneous alkenylene of sub- alkene, the miscellaneous alkenylene of sub- hydrocarbon, Asia
Alkynyl, cycloalkylene, sub- hydrocarbon ring alkylene base, sub- hydrocarbon ring alkylene alkylene, sub- alkene cycloalkylene, sub- alkene cycloalkanes support alkenylene, Asia
Hydrocarbon ring alkylene alkenylene, sub- alkynes cycloalkylene, sub- alkynes cycloalkanes support alkynylene, heterocycle alkylene base, sub- hydrocarbon heterocycle alkylene base, sub- hydrocarbon are miscellaneous
Cycloalkanes alkylene, sub- alkene heterocycle alkylene base, sub- alkene heterocycle alkane alkenylene, sub- hydrocarbon heterocycle alkane alkenylene, sub- alkynes heterocycle alkylene base, Asia
Alkynes heterocycle alkane alkynylene, cyclenes support group, sub- hydrocarbon ring alkene support group, sub- hydrocarbon ring alkene support alkylene, sub- alkene cyclenes support group, sub- alkene cyclenes support
Alkenylene, sub- hydrocarbon ring alkene support alkenylene, sub- alkynes cyclenes support group, sub- alkynes cyclenes support alkynylene, heterocycle alkene support group, sub- hydrocarbon heterocycle alkene support
Base, sub- hydrocarbon heterocycle alkene alkylene, sub- alkene heterocycle alkene support group, sub- alkene heterocycle alkene alkenylene, sub- hydrocarbon heterocycle alkene alkenylene, sub- alkynes heterocycle
Alkene support group, sub- alkynes heterocycle alkene alkynylene, fragrant support group, sub- hydrocarbon fragrance support group, sub- hydrocarbon fragrance support alkylene, sub- alkene fragrance support group,
Sub- alkene fragrance support alkenylene, sub- hydrocarbon fragrance support alkenylene, sub- alkynes fragrant support group, sub- alkynes fragrant support alkynylene, heteroaryl perfume (or spice) support group, Asia
Hydrocarbon heteroaryl perfume (or spice) support group, sub- hydrocarbon heteroaryl perfume (or spice) support alkylene, sub- alkene heteroaryl perfume (or spice) support group, sub- alkene heteroaryl perfume (or spice) support alkenylene, sub- hydrocarbon heteroaryl are fragrant
It supports in alkenylene, sub- alkynes heteroaryl perfume (or spice) support group, sub- alkynes heteroaryl perfume (or spice) support alkynylene, 1,4- alkyl substituted-piperazinyl, carbonyl or thiocarbonyl
Any one；R3 and R4 may be the same or different；
R1、R2、R3And R4In four groups, there are two or more than two groups contain unsaturated bond.
R1、R2、R3And R4In four groups, there are two or more than two groups contain unsaturated bond, the unsaturated bond
For carbon-carbon double bond, triple carbon-carbon bonds, carbon-to-nitrogen double bon, three key of three key of carbon nitrogen, nitrogen nitrogen double bond or nitrogen nitrogen etc..
R1And R2It can be with common adjacent carbon atom in the same ring structure.
Preferably, R1And R2It is fragrant independently to be hydrogen atom, alkyl, naphthenic base, heterocycle, Heterocyclylalkyl, aromatic radical, heteroaryl
Any one in base, alkane miscellaneous alkyl, alkylene or the sub- miscellaneous alkylene of hydrocarbon.
Preferably, R3And R4It independently is alkenylene, the miscellaneous alkenylene of sub- alkene, the miscellaneous alkenylene of sub- hydrocarbon, alkynylene, sub- alkene cycloalkanes
Support group, sub- alkene cycloalkanes support alkenylene, sub- hydrocarbon ring alkylene alkenylene, sub- alkynes cycloalkylene, sub- alkynes cycloalkanes support alkynylene, sub- alkene heterocycle
Alkylene base, sub- alkene heterocycle alkane alkenylene, sub- hydrocarbon heterocycle alkane alkenylene, sub- alkynes heterocycle alkylene base, sub- alkynes heterocycle alkane alkynylene, cyclenes
Support group, sub- hydrocarbon ring alkene support group, sub- hydrocarbon ring alkene support alkylene, sub- alkene cyclenes support group, sub- alkene cyclenes support alkenylene, sub- hydrocarbon ring alkene support are sub-
Alkenyl, sub- alkynes cyclenes support group, sub- alkynes cyclenes support alkynylene, heterocycle alkene support group, sub- hydrocarbon heterocycle alkene support group, sub- hydrocarbon heterocycle alkene Asia hydrocarbon
Base, sub- alkene heterocycle alkene support group, sub- alkene heterocycle alkene alkenylene, sub- hydrocarbon heterocycle alkene alkenylene, sub- alkynes heterocycle alkene support group, sub- alkynes heterocycle alkene
Alkynylene, sub- alkene fragrance support group, sub- alkene fragrance support alkenylene, sub- hydrocarbon fragrance support alkenylene, sub- alkynes fragrant support group, sub- alkynes fragrant support
Alkynylene, sub- alkene heteroaryl perfume (or spice) support group, sub- alkene heteroaryl perfume (or spice) support alkenylene, sub- hydrocarbon heteroaryl perfume (or spice) support alkenylene, sub- alkynes heteroaryl perfume (or spice) support group, Asia
Alkynes heteroaryl perfume (or spice) supports any one in alkynylene, 1,4- alkyl substituted-piperazinyl, carbonyl or thiocarbonyl.
In curing agent of the invention, R3(or R4) side connect with oxygen atom, the other side is connect with the end group of the molecule,
The end group can be carbon-carbon double bond, triple carbon-carbon bonds, carbon-to-nitrogen double bon, three key of carbon nitrogen, nitrogen nitrogen with unsaturated bond, the unsaturated bond
Three key of double bond or nitrogen nitrogen etc..The end group can also be without unsaturated bond.The present invention usesIndicate curing agent strand
End group.
Preferably, the olefin(e) compound accounts for the 5~95% of the compositions of thermosetting resin gross mass, preferably 35~
70%, such as 35%, 40%, 45%, 50%, 55%, 60%, 65%, 70%.
Preferably, the unsaturated bond in the thermosetting resin containing unsaturated bond is carbon-carbon double bond, triple carbon-carbon bonds, carbon
Nitrogen double bond, three key of three key of carbon nitrogen, nitrogen nitrogen double bond or nitrogen nitrogen etc..
Preferably, the thermosetting resin containing unsaturated bond carrys out acyl selected from polyphenylene oxide resin, cyanate resin, span
Any one in imines-cyanate resin, 1,2- polybutadiene, butadiene styrene resin or bismaleimide or at least two
Mixture.
Preferably, account for compositions of thermosetting resin total weight 5~95% containing unsaturated bond, such as 10%,
15%, 20%, 25%, 30%, 35%, 40%, 45%, 50%, 55%, 60%, 65%, 70%, 75%, 80%, 85% or
90%, preferably 30~65%.
Preferably, the polyphenylene oxide resin is the polyphenylene oxide resin containing unsaturated group in molecular structure, the insatiable hunger
It is vinyl, allyl, styryl, acrylate-based or alkynyl with group.
Preferably, the compositions of thermosetting resin further includes organic additive flame retardant, organic addition resistance
Firing agent is phosphorus flame retardant and/or halogenated flame retardant.
Preferably, the phosphorus flame retardant is phosphonitrile fire retardant, the agent of phosphate FRX fire-retardant, three (2,6- dimethyl benzenes
Base) phosphine, resorcinol bis- [two (2,6- 3,5-dimethylphenyl) phosphates], resorcinol tetraphenyldiphosphate, triphenyl phosphate
Or in bisphenol-A (diphenyl phosphoester) any one or at least two mixture.
Preferably, the halogenated flame retardant is deca-BDE, brominated styrene, brominated polycarbonate, decabrominated dipheny second
In the double tetrabromo phthalimides of alkane or ethylene any one or at least two mixture.
Preferably, organic additive flame retardant account for the 1~50% of compositions of thermosetting resin total weight, such as 5%,
10%, 15%, 20%, 25%, 30%, 35%, 40% or 45%, preferably 10%~30%.
Preferably, the compositions of thermosetting resin further includes filler and/or curing initiator.
Preferably, the filler accounts for the 5~80% of compositions of thermosetting resin total weight, for example, 10%, 20%, 30%,
40%, 50%, 60% or 70%, preferably 10%~30%.
Preferably, the filler be crystallization silicon powder, melting silicon powder, ball-shaped silicon micro powder, aluminium hydroxide, magnesium hydroxide,
Kaolin, talcum powder, calcium silicates, metal oxide, nitride, silicon carbide, titanium dioxide, mullite, hollow glass microbead, titanium
Sour potassium fiber, carborundum mono-crystal fiber, boron nitride fiber, alumina single crystal fiber, staple glass fibre, polytetrafluorethylepowder powder,
In pps powder, Polystyrene powder or butadiene-styrene rubber powder any one or at least two mixture.
Preferably, the metal oxide is any one in aluminium oxide, magnesia, bismuth oxide, boron oxide or beryllium oxide
Kind or at least two mixture.
Preferably, the nitride is boron nitride or/and silicon nitride.
Preferably, the curing initiator accounts for the 1~10% of compositions of thermosetting resin total weight, for example, 2%, 3%,
4%, 5%, 6%, 7%, 8% or 9%, preferably 2~5%.
Preferably, the curing initiator is benzoyl peroxide, cumyl peroxide, the tertiary fourth of perbenzoic acid
Ester, two-(tert-butylperoxyiso-propyl) benzene, 2,5- bis- (2- ethyihexanoylperoxy) -2,5- dimethylhexane or 2, (the 2- second of 5- bis-
Base hexanoyl peroxide) in -2,5- dimethyl -3- hexin etc. any one or at least two mixture.
" comprising " of the present invention, it is intended that it can also include other components, these other components especially except described group
Assign the compositions of thermosetting resin different characteristics.In addition to this, " comprising " of the present invention may be replaced by sealing
" for " of enclosed or " by ... form ".
For example, the compositions of thermosetting resin can also contain various additives, as concrete example, antioxygen can be enumerated
Agent, heat stabilizer, antistatic agent, ultraviolet absorbing agent, pigment, colorant or lubricant etc..These various additives can be single
It solely uses, two or more can also be used in mixed way.
The second object of the present invention is to provide a kind of resin adhesive liquid, is by compositions of thermosetting resin as described above
It is dissolved or dispersed in solvent and obtains.
It as the solvent in the present invention, is not particularly limited, as concrete example, the alcohol such as methanol, ethyl alcohol, butanol can be enumerated
Class, the ethers such as ethyl cellosolve, butyl cellosolve, ethylene glycol-methyl ether, carbitol, butyl carbitol, acetone, butanone, methyl second
The ketones such as base ketone, hexone, cyclohexanone, toluene, dimethylbenzene, mesitylene etc. are aromatic hydrocarbon, ethyoxyl second
The esters such as yl acetate, ethyl acetate, n,N-Dimethylformamide, n,N-dimethylacetamide, n-methyl-2-pyrrolidone etc.
Nitrogen-containing solvent.Above-mentioned solvent can be used alone, and two or more can also be used in mixed way, preferably toluene,
The aromatic hydrocarbon solvents such as dimethylbenzene, mesitylene and acetone, butanone, methyl ethyl ketone, hexone, cyclohexanone
Equal ketones flux is used in mixed way.
The third object of the present invention is to provide a kind of prepreg comprising reinforcing material and by impregnation it is dry after adhere to
Compositions of thermosetting resin as described above on reinforcing material.
The fourth object of the present invention is to provide a kind of laminate, the laminate contain at least one it is as described above pre-
Leaching material.
The fifth object of the present invention is to provide a kind of copper-clad laminate, and the copper-clad laminate includes at least one
Overlapping prepreg as described above and cover the prepreg after overlapping one or both sides copper foil.
Compared with the prior art, the invention has the following beneficial effects:
The present invention passes through olefin(e) compound of the selection containing two or more unsaturated bonds such as alkenyl and alkynyl and heat
Thermosetting resin cooperation has obtained a kind of with superior dielectric performance compositions of thermosetting resin.The compositions of thermosetting resin
On the basis of guaranteeing excellent dielectric properties, while being provided with outstanding heat resistance, production and processing performance and drill processability.
Compositions of thermosetting resin of the present invention is in addition to may be used as preparing resin sheet, resin laminated metal foil, pre-
It soaks except material, laminate, metal-clad laminate and printed wiring board, can also be used to prepare adhesive, coating, can also use
In building, aviation, ship and auto industry.
Specific embodiment
The technical scheme of the invention is further explained by means of specific implementation.
Embodiment 1
Use 55 parts of SA9000 polyphenylene oxide, 8 parts of olefin(e) compounds (A), 3 parts of cumyl peroxides, 13 parts of BT93 (ethylenes
Double tetrabromo phthalimides), 20 parts of SC2050MB, above compound is dissolved using toluene, and be modulated into suitable viscosity
Glue.2116 type E-glass cloth are infiltrated using this glue, and in 115 DEG C of baking ovens, remove solvent, obtain resin content
For 54% B-stage prepreg test sample.(ethylene is double by the SA9000, olefin(e) compound (A), cumyl peroxide, BT93
Tetrabromo phthalimide) and the sum of SC2050MB parts by weight be 100 parts.
The prepreg of eight above-mentioned preparations and one ounce of two panels of electrolytic copper foil are superimposed together, carried out by hot press
Lamination obtains doublesided copperclad laminate.Lamination is as follows: 1, at 80 DEG C~120 DEG C, heating rate is controlled 0.5 material temperature
DEG C~4.0 DEG C/min；2, pressure design 20kg/cm2；3, solidification temperature is 190 DEG C, and is kept for 90 minutes.Gained is two-sided
Copper-clad laminate is tested for the property, and respective performances are shown in Table 1.
CH2=CH-O-CH2- O-CH=CH2
(A)
Embodiment 2
Use 52 parts of SA9000 polyphenylene oxide, 10 parts of olefin(e) compounds (B), 3 parts of benzoyl peroxides, 15 parts of SPB-100 (phosphorus
Nitrile), 20 parts of SC2050MB, above compound is dissolved using toluene, and be modulated into the glue of suitable viscosity.It is soaked using this glue
Moisten 2116 type E-glass cloth, and in 115 DEG C of baking ovens, remove solvent, obtains the B-stage that resin content is 54% and presoak
Expect sample.The SA9000, olefin(e) compound (B), cumyl peroxide, SPB-100 (phosphonitrile) and SC2050MB parts by weight
The sum of number is 100 parts.
The prepreg of eight above-mentioned preparations and one ounce of two panels of electrolytic copper foil are superimposed together, carried out by hot press
Lamination obtains doublesided copperclad laminate.Lamination is as follows: 1, at 80 DEG C~120 DEG C, heating rate is controlled 0.5 material temperature
DEG C~4.0 DEG C/min；2, pressure design 20kg/cm2；3, solidification temperature is 190 DEG C, and is kept for 90 minutes.Gained is two-sided
Copper-clad laminate is tested for the property, and respective performances are shown in Table 1.
Embodiment 3~6
Doublesided copperclad laminate is prepared according to technique same as Example 1, specific formula and the performance test results are such as
Shown in table 1.
Comparative example 1
Using 33 parts of SA9000 polyphenylene oxide, 12 parts of Styrene-Butadiene block polymer, (triallyl is different by 22 parts of TAIC
Cyanurate), 3 parts of cumyl peroxides, 13 parts of BT93 (the double tetrabromo phthalimides of ethylene), 20 parts of SC2050MB,
Above compound is dissolved using toluene, and is modulated into the glue of suitable viscosity.2116 type electron level glass are infiltrated using this glue
Glass cloth, and in 115 DEG C of baking ovens, solvent is removed, the B-stage prepreg test sample that resin content is 54% is obtained.It is described
SA9000, Styrene-Butadiene block polymer, TAIC (Triallyl isocyanurate), cumyl peroxide, BT93
The sum of (the double tetrabromo phthalimides of ethylene) and SC2050MB parts by weight are 100 parts.
The prepreg of eight above-mentioned preparations and one ounce of two panels of electrolytic copper foil are superimposed together, carried out by hot press
Lamination obtains doublesided copperclad laminate.Lamination is as follows: 1, at 80 DEG C~120 DEG C, heating rate is controlled 0.5 material temperature
DEG C~4.0 DEG C/min；2, pressure design 20kg/cm2；3, solidification temperature is 190 DEG C, and is kept for 90 minutes.Gained is two-sided
Copper-clad laminate is tested for the property, and respective performances are shown in Table 1.
Comparative example 2
Use 32 parts of SA9000 polyphenylene oxide, 12 parts of thermoplastic polyphenylene ethers, 20 parts of TAIC (Triallyl isocyanurate), 3
Part cumyl peroxide, 13 parts of SPB-100 (phosphonitrile), 20 parts of SC2050MB, are dissolved above compound using toluene, and adjust
The glue of suitable viscosity is made.2116 type E-glass cloth are infiltrated using this glue, and in 115 DEG C of baking ovens, remove solvent,
Obtain the B-stage prepreg test sample that resin content is 54%.(triallyl is different by the SA9000, thermoplastic polyphenylene ethers, TAIC
Cyanurate), cumyl peroxide, the sum of SPB-100 (phosphonitrile) and SC2050MB parts by weight be 100 parts.
The prepreg of eight above-mentioned preparations and one ounce of two panels of electrolytic copper foil are superimposed together, carried out by hot press
Lamination obtains doublesided copperclad laminate.Lamination is as follows: 1, at 80 DEG C~120 DEG C, heating rate is controlled 0.5 material temperature
DEG C~4.0 DEG C/min；2, pressure design 20kg/cm2；3, solidification temperature is 190 DEG C, and is kept for 90 minutes.Gained is two-sided
Copper-clad laminate is tested for the property, and respective performances are shown in Table 1.
Comparative example 3
Use 42 parts of SA9000 polyphenylene oxide, 12 parts of 1,2- polybutadiene, 10 parts of BMI (bismaleimide), 3 parts of peroxidating
Benzoyl, 13 parts of decabromodiphenylethane, 20 parts of SC2050MB, are dissolved above compound using toluene, and are modulated into suitable glutinous
The glue of degree.2116 type E-glass cloth are infiltrated using this glue, and in 115 DEG C of baking ovens, remove solvent, resin is obtained and contains
The B-stage prepreg test sample that amount is 54%.SA9000,1,2- polybutadiene, BMI (bismaleimide), peroxidating
The sum of benzoyl, decabromodiphenylethane and SC2050MB parts by weight are 100 parts.
The prepreg of eight above-mentioned preparations and one ounce of two panels of electrolytic copper foil are superimposed together, carried out by hot press
Lamination obtains doublesided copperclad laminate.Lamination is as follows: 1, at 80 DEG C~120 DEG C, heating rate is controlled 0.5 material temperature
DEG C~4.0 DEG C/min；2, pressure design 20kg/cm2；3, solidification temperature is 190 DEG C, and is kept for 90 minutes.Gained is two-sided
Copper-clad laminate is tested for the property, and respective performances are shown in Table 1.
Gained doublesided copperclad laminate is tested for the property, respective performances are shown in Table 1.
The performance test results of copper-clad laminate obtained by 1 compositions of thermosetting resin of table
It can be seen that from the test result of upper table embodiment and comparative example using olefin(e) compound of the present invention, tool
There is more excellent dielectric properties (Dk value is lower), more preferably (resistance to immersed solder, PCT test long period can be not stratified for heat resistance
Plate bursting), prepreg fugitive constituent is also at a lower level, is easy to store for the customer, processing, and performance is steady
It is fixed.
The above performance test methods are as follows:
Dielectric constant (Dk), dielectric loss (Df): test uses IPC-TM-6502.5.5.9 method；
Tg: it is measured according to the DSC test method of IPC-TM-6502.4.25 defined.
Td: etching away copper foil for copper-clad laminate, substrate is tested using thermal gravimetric analyzer (TGA), nitrogen atmosphere
In, it is heated up with 10/min, the temperature value when thermal weight loss reaches 5% weight loss.
PCT: etching away copper foil for copper-clad laminate, place a substrate in steam pressure cooker, at 121 DEG C, under 2atm
After processing 2 hours, it is immersed in the tin furnace that temperature is 288 DEG C, the corresponding time is recorded when substrate occurs and blisters or be layered.When
Substrate did not occur blistering or being layered more than 5 minutes to terminate to evaluate in tin furnace.
Resistance to dip solderability evaluation: copper-clad laminate is immersed in in 288 DEG C of temperature of tin furnace taking-up after 20 seconds and is cooled to room
Then temperature is impregnated into tin furnace 5 times repeatedly again, resistance to dip solderability by observation ocular estimate.
Prepreg fugitive constituent: prepreg being put into 163 DEG C of baking oven, is toasted 30 minutes, and fugitive constituent is tested.
Water absorption rate: test uses IPC-TM-6502.6.2.1；
Certainly, the embodiment of the above, only preferred embodiments of the invention, the reality being not intended to limit the invention
Apply range, therefore all equivalent change or modifications done according to structure, feature and principle described in scope of the present invention patent, wrap
It includes in scope of the present invention patent.
The Applicant declares that the present invention is explained by the above embodiments method detailed of the invention, but the present invention not office
Be limited to above-mentioned method detailed, that is, do not mean that the invention must rely on the above detailed methods to implement.Technical field
Technical staff it will be clearly understood that any improvement in the present invention, equivalence replacement and auxiliary element to each raw material of product of the present invention
Addition, selection of concrete mode etc., all of which fall within the scope of protection and disclosure of the present invention.
Claims (24)
1. a kind of compositions of thermosetting resin for laminate, including thermosetting resin and olefinic compound containing unsaturated bond
Object, the olefin(e) compound have following molecular structural formula:
CH2=CH-O-CH2- O-CH=CH2Or
The olefin(e) compound accounts for the 5~95% of compositions of thermosetting resin gross mass；The thermosetting property containing unsaturated bond
Resin accounts for the 5~95% of compositions of thermosetting resin total weight；
The thermosetting resin containing unsaturated bond is in polyphenylene oxide resin, the thermosetting resin containing unsaturated bond
Unsaturated bond be carbon-carbon double bond or triple carbon-carbon bonds.
2. compositions of thermosetting resin as described in claim 1, which is characterized in that the olefin(e) compound accounts for thermosetting resin
The 35~70% of composition gross mass.
3. compositions of thermosetting resin as described in claim 1, which is characterized in that the thermosetting property tree containing unsaturated bond
Rouge accounts for the 30~65% of compositions of thermosetting resin total weight.
4. compositions of thermosetting resin as described in claim 1, which is characterized in that the polyphenylene oxide resin is in molecular structure
Polyphenylene oxide resin containing unsaturated group, the unsaturated group is vinyl, allyl, styryl, acrylate-based
Or alkynyl.
5. compositions of thermosetting resin as described in claim 1, which is characterized in that the compositions of thermosetting resin includes
Machine additive flame retardant, organic addition fire retardant are phosphorus flame retardant and/or halogenated flame retardant.
6. compositions of thermosetting resin as claimed in claim 5, which is characterized in that organic additive flame retardant accounts for thermosetting
The 1~50% of property resin combination total weight.
7. compositions of thermosetting resin as claimed in claim 6, which is characterized in that organic additive flame retardant accounts for thermosetting
The 10%~30% of property resin combination total weight.
8. compositions of thermosetting resin as claimed in claim 7, which is characterized in that the phosphorus flame retardant is that phosphonitrile is fire-retardant
Agent, the agent of phosphate FRX fire-retardant, three (2,6- 3,5-dimethylphenyl) phosphines, bis- [two (2,6- 3,5-dimethylphenyl) phosphoric acid of resorcinol
Ester], resorcinol tetraphenyldiphosphate, in triphenyl phosphate or bisphenol-A (diphenyl phosphoester) any one or extremely
Few two kinds of mixture.
9. compositions of thermosetting resin as claimed in claim 5, which is characterized in that the halogenated flame retardant is decabrominated dipheny
Ether, brominated styrene, brominated polycarbonate, any one in the double tetrabromo phthalimides of decabromodiphenylethane or ethylene
Or at least two mixture.
10. compositions of thermosetting resin as claimed in one of claims 1 to 9, which is characterized in that the thermosetting resin combination
Object includes filler and/or curing initiator.
11. compositions of thermosetting resin as claimed in claim 10, which is characterized in that the filler accounts for thermosetting resin combination
The 5~80% of object total weight.
12. compositions of thermosetting resin as claimed in claim 11, which is characterized in that the filler accounts for thermosetting resin combination
The 10%~30% of object total weight.
13. compositions of thermosetting resin as claimed in claim 10, which is characterized in that the filler is crystallization silicon powder, melts
Melt silicon powder, ball-shaped silicon micro powder, aluminium hydroxide, magnesium hydroxide, kaolin, talcum powder, calcium silicates, metal oxide, nitride,
Silicon carbide, mullite, hollow glass microbead, potassium titanate fibre, carborundum mono-crystal fiber, staple glass fibre, polytetrafluoroethylene powder
In end, pps powder, Polystyrene powder or butadiene-styrene rubber powder any one or at least two mixture.
14. compositions of thermosetting resin as claimed in claim 13, which is characterized in that the metal oxide be aluminium oxide,
In magnesia, bismuth oxide, boron oxide or beryllium oxide any one or at least two mixture.
15. compositions of thermosetting resin as claimed in claim 13, which is characterized in that the metal oxide is titanium dioxide
And/or alumina single crystal fiber.
16. compositions of thermosetting resin as claimed in claim 13, which is characterized in that the nitride be boron nitride or/and
Silicon nitride.
17. compositions of thermosetting resin as claimed in claim 13, which is characterized in that the nitride is boron nitride fiber.
18. compositions of thermosetting resin as claimed in claim 10, which is characterized in that the curing initiator accounts for thermosetting property tree
The 1~10% of oil/fat composition total weight.
19. compositions of thermosetting resin as claimed in claim 18, which is characterized in that the curing initiator accounts for thermosetting property tree
The 2~5% of oil/fat composition total weight.
20. compositions of thermosetting resin as claimed in claim 10, which is characterized in that the curing initiator is benzoyl peroxide
Formyl, cumyl peroxide, peroxidized t-butyl perbenzoate, two-(tert-butylperoxyiso-propyl) benzene, (the 2- ethyl of 2,5- bis-
Hexanoyl peroxide) -2,5- dimethylhexane or 2, it is any one in 5- bis- (2- ethyihexanoylperoxy) -2,5- dimethyl -3- hexin
Kind or at least two mixture.
21. a kind of resin adhesive liquid is by the compositions of thermosetting resin dissolution or dispersion as described in one of claim 1-20
It obtains in a solvent.
22. a kind of prepreg comprising reinforcing material and by impregnation be attached to after dry on reinforcing material such as claim
Compositions of thermosetting resin described in one of 1-20.
23. a kind of laminate, the laminate contains an at least prepreg as claimed in claim 22.
24. a kind of copper-clad laminate, the copper-clad laminate includes the as claimed in claim 22 of at least one overlapping
Prepreg and cover the prepreg after overlapping one or both sides copper foil.
Priority Applications (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410809856.3A CN105754318B (en) | 2014-12-19 | 2014-12-19 | A kind of compositions of thermosetting resin and its application |
| PCT/CN2015/079984 WO2016095437A1 (en) | 2014-12-19 | 2015-05-27 | Thermosetting resin composition and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410809856.3A CN105754318B (en) | 2014-12-19 | 2014-12-19 | A kind of compositions of thermosetting resin and its application |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN105754318A CN105754318A (en) | 2016-07-13 |
| CN105754318B true CN105754318B (en) | 2019-02-19 |
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| CN201410809856.3A Active CN105754318B (en) | 2014-12-19 | 2014-12-19 | A kind of compositions of thermosetting resin and its application |
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| CN (1) | CN105754318B (en) |
| WO (1) | WO2016095437A1 (en) |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106566155A (en) * | 2016-11-13 | 2017-04-19 | 惠州市大亚湾科翔科技电路板有限公司 | Insulation fire retardant for circuit board |
| TW201900836A (en) * | 2017-05-18 | 2019-01-01 | 德商漢高智慧財產控股公司 | Curable composition for drip sealant applications |
| CN111378212B (en) * | 2018-12-29 | 2022-06-28 | 广东生益科技股份有限公司 | Resin composition, prepreg containing resin composition and dielectric substrate for antenna |
| CN111253702B (en) * | 2020-03-30 | 2023-06-06 | 广东生益科技股份有限公司 | Resin composition, prepreg and circuit material using same |
Family Cites Families (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| ATE271577T1 (en) * | 1994-09-02 | 2004-08-15 | Henkel Corp | HEAT CURED RESINS MADE OF MALEIMIDES AND/OR VINYL DERIVATIVES |
| US6627704B2 (en) * | 1999-12-01 | 2003-09-30 | General Electric Company | Poly(arylene ether)-containing thermoset composition, method for the preparation thereof, and articles derived therefrom |
| US20020072585A1 (en) * | 2000-10-17 | 2002-06-13 | Industrial Technology Research Institute | PPE derivatives and resin composition having the same |
| JP4499344B2 (en) * | 2002-05-28 | 2010-07-07 | 株式会社日立製作所 | Resin composition and prepreg, laminate and multilayer printed circuit board using the same |
| US7329708B2 (en) * | 2004-08-18 | 2008-02-12 | General Electric Company | Functionalized poly(arylene ether) composition and method |
| US20070066710A1 (en) * | 2005-09-21 | 2007-03-22 | Peters Edward N | Method for electrical insulation and insulated electrical conductor |
| WO2008136351A1 (en) * | 2007-04-26 | 2008-11-13 | Hitachi Chemical Company, Ltd. | Thermosetting resin composition and optical member using cured product of the thermosetting resin composition |
| KR102023975B1 (en) * | 2012-03-16 | 2019-09-23 | 주식회사 다이셀 | Resin composition for fiber-reinforced composite material, prepreg, and fiber-reinforced composite material |
| JP5914812B2 (en) * | 2012-08-29 | 2016-05-11 | パナソニックＩｐマネジメント株式会社 | Modified polyphenylene ether, method for producing the same, polyphenylene ether resin composition, resin varnish, prepreg, metal-clad laminate, and printed wiring board |
-
2014
- 2014-12-19 CN CN201410809856.3A patent/CN105754318B/en active Active
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2015
- 2015-05-27 WO PCT/CN2015/079984 patent/WO2016095437A1/en active Application Filing
Also Published As
| Publication number | Publication date |
|---|---|
| CN105754318A (en) | 2016-07-13 |
| WO2016095437A1 (en) | 2016-06-23 |
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